Low-temperature and average-temperature refrigeration

ABSTRACT

Binary compositions of 2,3,3,3-tetrafluoropropene and difluoromethane, as a heat transfer fluid in compression, low-temperature and average temperature refrigeration systems, with exchangers operating in counterflow mode or in split flow mode with counterflow tendency. Also, to a heat transfer method. The binary compositions can replace R-404A and R-407C (ternary mixture containing 52 wt. % of HFC-134a, 25 wt. % of pentafluoroethane and 23 wt. % of difluoromethane) in compression-type heat-transfer systems with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.14/615,780, filed on Feb. 6, 2015, which is a divisional of U.S.application Ser. No. 13/391,405, filed on Feb. 29, 2012, which is a U.S.National Stage of International Application No. PCT/FR2010/051726, filedon Aug. 17, 2010, which claims the benefit of French Application No.09.56242, filed on Sep. 11, 2009. The entire contents of each of U.S.application Ser. No. 14/615,780, U.S. application Ser. No. 13/391,405,International Application No. PCT/FR2010/051726, and French ApplicationNo. 09.56242 are hereby incorporated herein by reference in theirentirety.

TECHNICAL FIELD

The present invention relates to the use of binary compositions of2,3,3,3-tetrafluoropropene and difluoromethane as heat transfer fluids.

BACKGROUND

The problems posed by substances with ozone depletion potential (ODP)were discussed in Montreal, where the protocol was signed requiring areduction of the production and use of chlorofluorocarbons (CFCs).Amendments have been made to this protocol, requiring abandonment ofCFCs and extending the regulations to cover other products, includinghydrochlorofluorocarbons (HCFCs).

The refrigeration and air-conditioning industry has made a considerableinvestment in substitution of these refrigerants, and accordinglyhydrofluorocarbons (HFCs) were put on the market.

In the automobile industry, the systems for air conditioning of vehiclesmarketed in many countries have changed over from a chlorofluorocarbonrefrigerant (CFC-12) to a hydrofluorocarbon refrigerant(1,1,1,2-tetrafluoroethane: HFC-134a), which is less harmful to theozone layer. However, with respect to the objectives established by theKyoto protocol, HFC-134a (GWP=1300) is considered to have a high warmingpower. A fluid's contribution to the greenhouse effect is quantified bya criterion, GWP (Global Warming Potential), which summarizes thewarming power by taking a reference value of 1 for carbon dioxide.

As carbon dioxide is nontoxic, nonflammable and has a very low GWP, ithas been proposed as a refrigerant for air-conditioning systems in placeof HFC-134a. However, the use of carbon dioxide has several drawbacks,notably connected with the very high pressure for its application asrefrigerant in existing equipment and technologies.

Moreover, the mixture R-404A consisting of 44 wt. % ofpentafluoroethane, 52 wt. % of trifluoroethane and 4 wt. % of HFC-134ais widely used as refrigerant for large areas (supermarkets) and inrefrigerated transport. However, this mixture has a GWP of 3900.

Document JP 4110388 describes the use of hydrofluoropropenes of formulaC₃H_(m)F_(n), with m, n representing an integer between 1 and 5inclusive and m+n=6, as heat transfer fluids, in particulartetrafluoropropene and trifluoropropene.

Document WO2004/037913 discloses the use of compositions comprising atleast one fluoroalkene having three or four carbon atoms, notablypentafluoropropene and tetrafluoropropene, preferably having a GWP of atmost 150, as heat transfer fluids.

Document WO 2006/094303 discloses an azeotropic composition containing7.4 wt. % of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 92.6 wt. % ofdifluoromethane (HFC-32). This document also discloses quasi-azeotropiccompositions containing from 1 to 57 wt. % of 2,3,3,3-tetrafluoropropeneand from 43 to 99 wt. % of difluoromethane.

A heat exchanger is a device for transferring thermal energy from onefluid to another, without mixing them. The thermal flux passes throughthe exchange surface that separates the fluids. Mostly this method isused for cooling or heating a liquid or a gas that cannot be cooled orheated directly.

In compression systems, heat exchange between the refrigerant and theheat sources takes place via heat-transfer fluids. These heat-transferfluids are in the gaseous state (the air in air conditioning anddirect-expansion refrigeration), liquid (water in domestic heat pumps,glycol solution) or two-phase.

There are various transfer modes:

-   -   the two fluids are arranged in parallel and go in the same        direction co-current mode (antimethodical);    -   the two fluids are arranged in parallel but go in the opposite        direction countercurrent mode (methodical);    -   the two fluids are positioned perpendicularly: crossed-current        mode. The crossed current can have co-current or countercurrent        tendency;    -   one of the two fluids makes a U-turn in a wider pipeline, which        the second fluid passes through. This configuration is        comparable to a co-current exchanger on half its length, and to        a countercurrent exchanger for the other half: pin-head mode.

DETAILED DESCRIPTION

The applicant has now discovered that binary compositions of2,3,3,3-tetrafluoropropene and difluoromethane are particularlyadvantageous as heat transfer fluid in compression systems forlow-temperature and medium-temperature refrigeration, with exchangersoperating in countercurrent mode or in crossed-current mode withcountercurrent tendency.

Thus, these compositions can be used as heat transfer fluid in therefrigeration of refrigerated vehicles, in food storage and in industry(chemical industry, food industry etc.) with exchangers incountercurrent mode or in crossed-current mode with countercurrenttendency.

A first object of the present invention relates to the use of binarycompositions of 2,3,3,3-tetrafluoropropene and difluoromethane as heattransfer fluid in compression systems for low-temperature andmedium-temperature refrigeration, with exchangers operating incountercurrent mode or in crossed-current mode with countercurrenttendency.

Low-temperature and medium-temperature refrigeration means the rangefrom −45° C. to −10° C. at the evaporator.

Preferably, the binary compositions of 2,3,3,3-tetrafluoropropene anddifluoromethane contain essentially from 61 to 85 wt. % of2,3,3,3-tetrafluoropropene and from 15 to 39 wt. % of difluoromethane.

Advantageously, binary compositions contain essentially from 70 to 79wt. % of 2,3,3,3-tetrafluoropropene and from 21 to 30 wt. % ofdifluoromethane.

The binary compositions used in the present invention have both a zeroODP and a low GWP. The coefficient of performance (COP: ratio of thecold power to the electricity consumption of a refrigerator) of thesebinary compositions in exchangers in countercurrent mode is higher thanfor the compositions currently used in low-temperature andmedium-temperature refrigeration. Taking into account the pressure levelat the condenser, it is not necessary to develop new compressors; thecompressors currently on the market may be suitable.

The binary compositions used in the present invention can replace R-404Aand R-407C (ternary mixture containing 52 wt. % of HFC-134a, 25 wt. % ofpentafluoroethane and 23 wt. % of difluoromethane) in compression-typeheat-transfer systems with exchangers operating in countercurrent modeor in crossed-current mode with countercurrent tendency.

The binary compositions used according to the present invention can bestabilized. The amount of stabilizer preferably represents at most 5 wt.% relative to the binary composition.

As stabilizers, we may notably mention nitromethane, ascorbic acid,terephthalic acid, azoles such as tolutriazole or benzotriazole,phenolic compounds such as tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (alkyloptionally fluorinated or perfluorinated or alkenyl or aromatic) such asn-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidylether, butylphenylglycidyl ether, phosphites, phosphates, phosphonates,thiols and lactones.

A second object of the present invention relates to a method of heattransfer in compression systems for low- and medium-temperaturerefrigeration in which binary compositions of 2,3,3,3-tetrafluoropropeneand difluoromethane, as defined above, are used as refrigerant withexchangers operating in countercurrent mode or in crossed-current modewith countercurrent tendency.

The method according to the present invention can be employed in thepresence of lubricants such as mineral oil, alkylbenzene, polyalkyleneglycol, polyol ester and polyvinyl ether.

Experimental Section Tools for Calculation

The RK-Soave equation is used for calculating the densities, enthalpies,entropies and the data on liquid-vapor equilibrium of the mixtures. Touse this equation it is necessary to know the properties of the puresubstances used in the mixtures in question as well as the coefficientsof interaction for each binary mixture.

The data required for each pure substance are:

Boiling point, critical temperature and pressure, curve of pressure as afunction of temperature from the boiling point to the critical point,the saturated liquid density and saturated vapor density as a functionof temperature.

HFC-32:

The data for HFC-32 are published in ASHRAE Handbook 2005 chapter 20,and are also available using Refrop (software developed by NIST forcalculating the properties of refrigerants).

HFO-1234yf:

The data for the temperature-pressure curve of HFO-1234yf are measuredby the static method. The critical temperature and pressure are measuredwith a C80 calorimeter marketed by Setaram. The densities, at saturationas a function of temperature, are measured by the vibrating tubedensimeter technology developed by the laboratories of the Ecole deMines (“Mining Engineering College”) in Paris.

Coefficient of Binary Interaction of HFC-32/HFO-1234yf:

The RK-Soave equation uses coefficients of binary interaction forrepresenting the behavior of the products in mixtures. The coefficientsare calculated as a function of experimental data for liquid-vaporequilibrium.

The technique used for the measurements of liquid-vapor equilibrium isthe static analytical cell method. The equilibrium cell comprises asapphire tube and is equipped with two ROLSITM electromagnetic samplers.It is immersed in a cryothermostat bath (HUBER HS40). Magnetic stirringdriven by a field rotating at variable speed is used for acceleratingattainment of the equilibria. The samples are analyzed by gaschromatography (HP5890 series II) using a catharometer (TCD).

The measurements of liquid-vapor equilibrium on the HFC-32/HFO-1234yfbinary mixture are performed for the following isotherms: −10° C., 30°C. and 70° C.

Compression System

Consider a compression system equipped with an evaporator andcountercurrent condenser, a screw compressor and a pressure reducingvalve.

The system functions with 15° C. of superheating and 5° C. ofsupercooling. The minimum temperature difference between the secondaryfluid and the refrigerant is considered to be of the order of 5° C.

The isoentropic efficiency of the compressors is a function of thecompression ratio. This efficiency is calculated from the followingequation:

$\begin{matrix}{\eta_{isen} = {a - {b\left( {\tau - c} \right)}^{2} - \frac{d}{\tau - e}}} & (1)\end{matrix}$

For a screw compressor, the constants a, b, c, d and e in equation (1)of isoentropic efficiency are calculated on the basis of the standarddata published in the Handbook “Handbook of air conditioning andrefrigeration”, page 11.52.

The coefficient of performance (COP) is defined as the ratio of theuseful power delivered by the system to the power supplied to orconsumed by the system.

The Lorenz coefficient of performance (COP_(Lorenz)) is a referencecoefficient of performance. It is a function of temperature and is usedfor comparing the COPs of different fluids.

The Lorenz coefficient of performance is defined as follows:

(The temperatures T are in K)

T _(mean) ^(condenser) =T _(inlet) ^(condenser) −T _(outlet)^(condenser)  (2)

T _(mean) ^(evaporator) =T _(outlet) ^(evaporator) −T _(inlet)^(evaporator)  (3)

The COP_(Lorenz) in the case of air conditioning and refrigeration is:

$\begin{matrix}{{COPlorenz} = \frac{T_{mean}^{evaporator}}{T_{mean}^{condenser} - T_{mean}^{evaporator}}} & (4)\end{matrix}$

The Lorenz COP in the case of heating is:

$\begin{matrix}{{COPlorenz} = \frac{T_{mean}^{condenser}}{T_{mean}^{condenser} - T_{mean}^{evaporator}}} & (5)\end{matrix}$

For each composition, the coefficient of performance of the Lorenz cycleis calculated as a function of the corresponding temperatures.

% COP/COP_(Lorenz) is the ratio of the COP of the system relative to theCOP of the corresponding Lorenz cycle.

Results, Low-Temperature Refrigeration Mode

In low-temperature mode, the compression system operates between arefrigerant inlet temperature at the evaporator of −30° C. and arefrigerant inlet temperature at the condenser of 40° C. The systemdelivers cold at −25° C.

The performance of the compositions according to the invention inlow-temperature operating conditions is given in Table 1. The values ofthe constituents (HFO-1234yf, HFC-32) for each composition are given aspercentage by weight.

TABLE 1 Temp outlet Temp outlet T outlet evap cond Ratio efficiency %COP/ evap (° C.) comp (° C.) cond (° C.) P (bar) P (bar) (w/w) Shiftcomp COPLorenz R404A −30 100 40 2.1 18.1 8.8 0.45 53.8 31.8 HFO-1234yfHFC-32 80 20 −25 102 32 1.7 13.8 8.2 4.98 58.4 39.3 79 21 −25 102 32 1.714.0 8.2 5.06 58.7 39.6 78 22 −25 103 32 1.7 14.2 8.1 5.13 59.0 39.8 7723 −25 103 32 1.8 14.4 8.1 5.19 59.2 40.0 76 24 −25 104 32 1.8 14.6 8.15.23 59.4 40.1 75 25 −25 104 33 1.8 14.8 8.1 5.25 59.6 40.3 74 26 −25105 33 1.9 15.0 8.0 5.26 59.7 40.4 73 27 −25 106 33 1.9 15.2 8.0 5.2659.8 40.4 72 28 −25 107 33 1.9 15.4 8.0 5.24 59.9 40.5 71 29 −25 108 332.0 15.6 8.0 5.21 60.0 40.5 70 30 −25 108 33 2.0 15.8 8.0 5.17 60.0 40.565 35 −25 114 34 2.1 16.8 8.0 4.84 59.8 40.3 61 39 −26 118 34 2.2 17.68.1 4.45 59.3 40.0

Results, Medium-Temperature Refrigeration Mode

In medium-temperature mode, the compression system operates between arefrigerant inlet temperature at the evaporator of −15° C. and arefrigerant inlet temperature at the condenser of 35° C. The systemdelivers cold at −10° C.

The performance of the binary compositions in medium-temperatureoperating conditions is given in Table 2. The values of the constituents(HFO-1234yf, HFC-32) for each composition are given as percentage byweight.

TABLE 2 Temp outlet Temp outlet T outlet evap cond Ratio efficiency %COP/ evap (° C.) comp (° C.) cond (° C.) P (bar) P (bar) (w/w) Shiftcomp COPLorenz R404A −15 62 35 3.7 16.0 4.4 0.46 79.9 54.9 HFO-1234yfHFC-32 80 20 −9 64 27 3.2 12.2 3.8 6.11 81.3 61.9 79 21 −9 64 27 3.212.3 3.8 6.16 81.3 62.0 78 22 −9 65 27 3.3 12.5 3.8 6.19 81.3 62.0 77 23−9 65 27 3.3 12.7 3.8 6.20 81.3 61.9 76 24 −9 66 27 3.4 12.9 3.8 6.2081.3 61.9 75 25 −9 66 27 3.4 13.0 3.8 6.18 81.3 61.9 73 27 −9 67 28 3.513.4 3.8 6.10 81.3 61.8 72 28 −9 68 28 3.5 13.6 3.8 6.05 81.3 61.8 71 29−9 69 28 3.6 13.7 3.8 5.98 81.3 61.7 70 30 −9 69 28 3.6 13.9 3.8 5.9081.3 61.6

1. The use of a binary composition containing 2,3,3,3-tetrafluoropropeneand difluoromethane as heat transfer fluid in compression-type, low- andmedium-temperature refrigeration systems, with exchangers operating incountercurrent mode or in crossed-current mode with countercurrenttendency.
 2. The use as claimed in claim 1, characterized in that thecomposition contains essentially from 61 to 85 wt. % of2,3,3,3-tetrafluoropropene and from 15 to 39 wt. % of difluoromethane.3. The use as claimed in claim 1, characterized in that the compositioncontains essentially from 70 to 79 wt. % of 2,3,3,3-tetrafluoropropeneand from 21 to 30 wt. % of difluoromethane.
 4. A method of heat transferin which a binary composition containing 2,3,3,3-tetrafluoropropene anddifluoromethane is used as refrigerant in compression-type low- andmedium-temperature refrigeration systems, with exchangers operating incountercurrent mode or in crossed-current mode with countercurrenttendency.
 5. The method as claimed in claim 4, characterized in that thecomposition contains essentially from 61 to 85 wt. % of2,3,3,3-tetrafluoropropene and from 15 to 39 wt. % of difluoromethane.6. The method as claimed in claim 4, characterized in that thecomposition contains essentially from 70 to 79 wt. % of2,3,3,3-tetrafluoropropene and from 21 to 30 wt. % of difluoromethane.7. The method as claimed in claim 4, characterized in that the binarycomposition is stabilized.
 8. The method as claimed in claim 4,characterized in that it is implemented in the presence of a lubricant.